WO2015067563A1 - Flame retardant led for indoor lighting - Google Patents
Flame retardant led for indoor lighting Download PDFInfo
- Publication number
- WO2015067563A1 WO2015067563A1 PCT/EP2014/073586 EP2014073586W WO2015067563A1 WO 2015067563 A1 WO2015067563 A1 WO 2015067563A1 EP 2014073586 W EP2014073586 W EP 2014073586W WO 2015067563 A1 WO2015067563 A1 WO 2015067563A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- acid
- flame retardant
- polymer composition
- polymer
- part according
- Prior art date
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 44
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 15
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Classifications
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- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
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- H10H20/00—Individual inorganic light-emitting semiconductor devices having potential barriers, e.g. light-emitting diodes [LED]
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- C08L2203/00—Applications
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- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- C08L2207/00—Properties characterising the ingredient of the composition
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
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- C08L2666/78—Stabilisers against oxidation, heat, light or ozone
- C08L2666/80—Metal-containing stabilizers
Definitions
- the present invention relates to flame retardant Light Emitting Diode devices (LED) and more particularly to LED's made from a polymer composition (C) comprising at least one polymer selected from the group consisting of a polyamide, a polyester, an epoxy and a silicon resin, a flame retardant system and magnesium oxide.
- a polymer composition comprising at least one polymer selected from the group consisting of a polyamide, a polyester, an epoxy and a silicon resin, a flame retardant system and magnesium oxide.
- thermoplastic compound formulations used for their manufacture to impart flame retardancy in addition to performance
- characteristics including electrical conductivity, electrical insulativity, processability, reflectance retention after heat and/or light exposure and mechanical strength.
- thermoplastic compounds can be introduced into thermoplastic compounds to improve their flammability ratings. Introducing flame retardants into thermoplastic compounds helps impart ignition resistance and inhibits or resists the spread of fire. This added property allows for thermoplastic compounds to be utilized safely where a potential for fire exists, meeting the requirements of Underwriter Labs UL-94 and the International Electrotechnical Commission (IEC).
- IEC International Electrotechnical Commission
- thermoplastic compounds do not result in the production of compounds suitable for the manufacture of LED' s and in particular for the manufacture of LED reflectors. It appeared very difficult to obtain a compound featuring flame resistance and high light reflectance at the same time.
- US 2010/270577 relates to polyamide compounds suitable for the manufacture of plastic components for use in a lighting system such as a LED.
- US' 577 discloses the possibility of adding a flame retardant system to the compound which may comprise a halogenated flame retardant and/or a halogen free flame retardant, and next it an optional a flame retardant synergist.
- US' 577 only discloses and exemplifies a brominated polystyrene as flame retardant and zinc borate as synergist.
- US' 577 does not disclose neither the flame resistance nor the reflectance performance of the compounds exemplified.
- the present invention relates to a part of a Light Emitting Diode device comprising a polymer composition (C) comprising :
- polymer (P) selected from the group consisting of a polyamide, a polyester, an epoxy and a silicon resin;
- composition (C), of a flame retardant system from 5 to 40 wt. %, based on the total weight of the composition (C), of a flame retardant system ;
- composition (C) from 1 to 7 wt. %, based on the total weight of the composition (C), of magnesium oxide.
- the polymer composition (C) of the present invention comprises three essential ingredients that are described in detail here below :
- the polymer (P) is the polymer (P)
- the polymer composition (C) of the present invention comprises at least one polymer (P) selected from the group consisting of a polyamide, a polyester, an epoxy and a silicon resin.
- the polymer (P) is preferably a polyamide.
- polyamide is intended to denote any polymer which comprises recurring units (R PA ) which are derived from the polycondensation of at least one dicarboxylic acid component (or derivative thereof) and at least one diamine component, and/or from the polycondensation of aminocarboxylic acids and/or lactams.
- amide-forming derivatives include a mono- or di-alkyl ester, such as a mono- or di-methyl, ethyl or propyl ester, of such carboxylic acid; a mono- or di-aryl ester thereof; a mono- or di-acid halide thereof; and a mono-or di-acid amide thereof, a mono- or di-carboxylate salt.
- the polyamide of the polymer is N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-(2-aminoethyl)-2-aminoethyl-N-amide
- composition (C) comprises at least 50 mol %, preferably at least 60 mol %, more preferably at least 70 mol %, still more preferably at least 80 mol % and most preferably at least 90 mol % of recurring units (R PA ).
- Excellent results were obtained when the polyamide of the polymer composition (C) consisted of recurring units (R PA ).
- the nature and quantities of the dicarboxylic acid component, the diamine component, and/or the aminocarboxylic acids and/or lactams has a great impact on the amorphous or semi-crystalline behaviour of the overall polyamide.
- the polyamide of the polymer composition (C) is preferably an aromatic polyamide polymer.
- aromatic polyamide polymer is intended to denote a polyamide which comprises more than 35 mol %, preferably more than 45 mol %, more preferably more than 55 mol %, still more preferably more than 65 mol % and most preferably more than 75 mol % of recurring units (R PA ) which are aromatic recurring units.
- R PA recurring units
- aromatic recurring unit is intended to denote any recurring unit that comprises at least one aromatic group.
- the aromatic recurring units may be formed by the polycondensation of at least one aromatic dicarboxylic acid with an aliphatic diamine or by the polycondensation of at least one aliphatic dicarboxylic acid with an aromatic diamine, or by the polycondensation of aromatic
- a dicarboxylic acid or a diamine is considered as "aromatic" when it comprises one or more than one aromatic group.
- Non limitative examples of aromatic dicarboxylic acids are notably phthalic acids, including isophthalic acid (IA), terephthalic acid (TA) and orthophthalic acid (OA), 2,5-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,2-bis(4-carboxyphenyl)propane, bis(4-carboxyphenyl)methane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)ketone, 4,4'-bis(4-carboxyphenyl)sulfone,
- IA isophthalic acid
- TA terephthalic acid
- OA orthophthalic acid
- 2,5-pyridinedicarboxylic acid 2,4-pyridinedicarboxylic acid
- 3,5-pyridinedicarboxylic acid 3,5-pyridinedicarboxylic acid
- oxalic acid [HOOC-COOH, malonic acid (HOOC-CH 2 -COOH), adipic acid [HOOC-(CH 2 ) 4 -COOH], succinic acid [HOOC-(CH 2 ) 2 -COOH], glutaric acid [HOOC-(CH 2 ) 3 -COOH], 2,2-dimethyl-glutaric acid
- the dicarboxylic acid is preferably aromatic and comprises advantageously at least one phthalic acid selected from the group consisting of isophthalic acid (IA) and terephthalic acid (TA).
- IA isophthalic acid
- TA terephthalic acid
- Isophthalic acid and terephthalic acid can be used alone or in combination.
- the phthalic acid is preferably terephthalic acid, optionally in combination with isophthalic acid.
- Non limitative examples of aliphatic diamines are typically aliphatic alkylene diamines having 2 to 18 carbon atoms, which are advantageously selected from the group consisting of 1 ,2-diaminoethane, 1 ,2-diaminopropane, propylene- 1,3-diamine, 1,3-diamino butane, 1 ,4-diamino butane,
- 1,10-diaminodecane 1,10-diaminodecane, 1.8-diamino-l,3-dimethyloctane, l,8-diamino-l,4- dimethyloctane, 1.8-diamino-2,4-dimethyloctane, 1 ,8-diamino-3,4- dimethyloctane, 1.8-diamino-4,5-dimethyloctane, 1.8-diamino-2,2- dimethyloctane, 1.8-diamino-3,3-dimethyloctane, 1 ,8-diamino-4,4- dimethyloctane, 1 ,6-diamino-2,4-diethylhexane, 1 ,9-diamino-5-methylnonane, 1,11-diaminoundecane and 1,12-diamin
- the aliphatic diamine may be chosen from cycloaliphatic diamines such as isophorone diamine (also known as 5-amino-(l-aminomethyl)-l,3,3- trimethylcyclohexane), 1 ,3-cyclohexanebis(methylamine) (1 ,3-BAMC),
- isophorone diamine also known as 5-amino-(l-aminomethyl)-l,3,3- trimethylcyclohexane
- 1 ,3-cyclohexanebis(methylamine) (1 ,3-BAMC)
- the aliphatic diamine is preferably selected from the group consisting of 1,6-diaminohexane (also known as hexamethylene diamine), 1,9-diaminononane,
- aromatic diamines mention can be notably made of meta- phenylene diamine (MPD), para-phenylene diamine (PPD),
- the aromatic diamine is preferably meta-xylylene diamine (MXDA).
- aromatic aminocarboxylic acids or derivatives thereof may also be used for the manufacture of the polyamide of the polymer
- composition (C) which is generally selected from the group consisting of 4-(aminomethyl)benzoic acid and 4-aminobenzoic acid, 6-aminohexanoic acid, l-aza-2-cyclononanone, l-aza-2-cyclododecanone, 11-aminoundecanoic acid, 12-aminododecanoic acid, 4-(aminomethyl)benzoic acid, cis-4- (aminomethyl)cyclohexanecarboxylic acid, trans-4-
- Non limitative examples of polyamides of the polymer composition (C) are : the polymer of adipic acid with meta-xylylene diamine (also known as PAMXD6 polymers, which are notably commercially available as IXEF ® polyarylamides from Solvay Specialty Polymers U.S.A, L.L.C.), the polymers of phthalic acid, chosen among isophthalic acid (IA) and terephthalic acid (TA) and at least one aliphatic diamine such as 1,6-diaminohexane (notably commercially available as AMODEL ® polyphthalamides from Solvay Specialty Polymers U.S.A, L.L.C.), the polymer of terephthalic acid with 1 ,9-nonamethylene diamine, the polymer of terephthalic acid with 1,10-decamethylene diamine, the polymer of terephthalic acid with dodecamethylene diamine, the polymer of
- hexamethylene diamine and bis-l,3-aminomethylcyclohexane the copolymer of hexamethylene diamine with terephthalic acid and 2,6-napthalenedicarboxylic acid; the copolymer of hexamethylene diamine with terephthalic acid and sebacic acid; the copolymer of hexamethylene diamine with terephthalic acid and 1,12-diaminododecanoic acid; the copolymer of hexamethylene diamine with terephthalic acid, isophthalic acid and 1 ,4-cyclohexanedicarboxylic acid; the copolymer of decamethylene diamine with terephthalic acid and
- decamethylene diamine with 1,4-cyclohexanedicarboxylic acid the copolymer of hexamethylene diamine with 11-amino-undecanoic acid and
- 2,6-napthalenedicarboxylic acid the copolymer of terephthalic acid with hexamethylene diamine and 2-methylpentamethylene diamine; the copolymer of terephthalic acid with decamethylene diamine and 2-methylpentamethylene diamine; the copolymer of 2,6-napthalenedicarboxylic with hexamethylene diamine and 2-methylpentamethylene diamine; the copolymer of
- the polyamide is a polyphthalamide, i.e. a polyamide which comprises recurring units (R PPA ) which are derived from the polycondensation of at least one phthalic acid.
- R PPA recurring units
- phthalic acid is used to refer to anyone of isophthalic acid, terephthalic acid and orthophthalic acid.
- the polyamide is selected from the group consisting of the polymer of adipic acid with meta-xylylene diamine, the polymer of terephthalic acid with
- 1,10-decamethylene diamine 1,10-decamethylene diamine
- the copolymer of terephthalic acid and optionally isophthalic acid with hexamethylene diamine the copolymer of terephthalic acid with hexamethylene diamine and decamethylene diamine and the copolymer of terephthalic acid and isophthalic acid with hexamethylene diamine and decamethylene diamine.
- the melting point of the polyamide of the polymer composition (C) is preferably of at least 260°C, preferably at least 280°C, more preferably at least 300°C and most preferably at least 310°C.
- polyamides polymers of phthalic acid chosen among isophthalic acid (IA) and terephthalic acid (TA) and at least one aliphatic diamine such as 1,6-diaminohexane.
- the polymer (P) is preferably a polyester.
- dicarboxylic acid is intended to include dicarboxylic acids and any derivative of dicarboxylic acids, including their associated acid halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof.
- the polyester comprises at least 50 mol %, preferably at least 60 mol %, more preferably at least 70 mol %, still more preferably at least 80 mol % and most preferably at least 90 mol % of recurring units comprising, in addition to the at least one ester moiety, at least one cycloaliphatic group.
- Excellent results were obtained when the polyester was essentially composed of recurring units comprising at least one ester moiety and at least one cycloaliphatic group.
- the cycloaliphatic group may derive from monomers (M A ), monomers (M B ), monomers (Mc) or monomers (M D ) comprising at least one group which is both aliphatic and cyclic.
- Non limitative examples of monomers (M A ) include lactide and
- Non limitative examples of monomers (M B ) include gly colic acid, 4-hydroxybenzoic acid and 6-hydroxynaphthalene-2-carboxylic acid.
- Non limitative examples of monomers (Mc) include
- 1,4-cyclohexanedimethanol ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2,2,4-trimethyl 1,3-pentanediol, 2,2,4,4-tetramethyl-l,3-cyclobutanediol, and neopentyl glycol, while 1,4-cyclohexanedimethanol and neopentyl glycol are preferred.
- Non limitative examples of monomers (M D ) include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acids, 1,4-cyclohexane dicarboxylic acid, succinic acid, sebacic acid, and adipic acid, while terephthalic acid and 1 ,4-cyclohexane dicarboxylic acid are preferred.
- polyester is a copolymer
- monomers (Mc) and (M D ) are preferably used.
- monomer (M c ) is preferably
- 1,4-cyclohexanedimethanol and monomer (M D ) is preferably a mixture of terephthalic acid and 1 ,6-naphthalene dicarboxylic acid.
- polyester When the polyester is a homopolymer, it may be selected from
- PCT poly(cyclohexylenedimethylene terephthalate)
- PCN poly(cyclohexylenedimethylene naphthalate)
- PCT poly(cyclohexylenedimethylene naphthalate)
- PCT i.e. a homopolymer obtained through the polycondensation of terephthalic acid with 1,4-cyclohexylenedimethanol.
- the polyester has advantageously an intrinsic viscosity of from about 0.4 to about 2.0 dl/g as measured in a 60:40 phenol/tetrachloroethane mixture or similar solvent at about 30°C.
- Particularly suitable polyester (P) for this invention has an intrinsic viscosity of 0.5 to 1.4 dl/g.
- the polyester has a melting point, as measured by DSC according to ISO-11357-3, of advantageously at least 250°C, preferably at least 260°C, more preferably at least 270°C and most preferably at least 280°C. Besides, its melting point is advantageously of at most 350°C, preferably at most 340°C, more preferably at most 330°C and most preferably at most 320°C. Excellent results were obtained with a polyester (P) having a melting point ranging from 280°C to 320°C.
- the polyester is preferably present in an amount of at least 40 wt. %, more preferably at least 45 wt. %, still more preferably at least 47 wt. %, and most preferably at least 48 wt. %, based on the total weight of the polymer
- composition (C) The polyester is also present in an amount of advantageously at most 80 wt. %, preferably at most 75 wt. %, more preferably at most 70 wt. %, still more preferably at most 65 wt. %, and most preferably at most 60 wt. %, based on the total weight of the polymer composition (C). Excellent results were obtained when the polyester was present in the polymer composition (C) in an amount from about 45 to about 60 wt. %, preferably from about 48 to
- the polymer (P) is preferably an epoxy resin.
- Epoxy resins are generally compounds with terminal, and/or internal
- epoxy resin is intended to denote resin having advantageously at least two epoxy groups, preferably two to six epoxy groups.
- the epoxy compounds having 2 to 4 epoxy groups are particularly preferred.
- Said epoxy compounds may be in any solid, semi-solid or liquid form.
- epoxy or epoxide
- 1,2-epoxy or epoxide
- vicinal epoxy or epoxide
- oxirane group is also art recognized terms for this epoxy group.
- Suitable epoxy resins may be saturated, unsaturated, cycloaliphatic, alicyclic or heterocyclic.
- Particularly suitable epoxy compounds are for example based on reaction products of polyfunctional alcohols, phenols, cycloaliphatic carboxylic acids, aromatic amines, or aminophenols with epichlorohydrin, or else cycloaliphatic epoxides or cycloaliphatic epoxyesters. It is also possible to use a mixture of various epoxy resins.
- compound E is choosen among triglycidyl ether of p-aminophenol (or 4-(2,3-epoxypropoxy)- N,N-bis(2,3-epoxy-propyl)aniline), triglycidyl ether of meta-aminophenol (or 3-(2,3-epoxypropoxy) N,N-bis(2,3-epoxypropyl)aniline)and triglycidylether of tris(4-hydroxyphenyl) methane.
- Particular preferred epoxy resin is triglycidyl ether of para-aminophenol.
- the epoxy resin is generally present in the polymer composition (C) in an amount of at least 30 wt. %, preferably of at least 40 wt. %, more preferably of at least 50 wt. %, and most preferably of at least 60 wt. %, based on the total weight of the composition (C). It is further understood that the wt. % of the epoxy resin in the polymer composition (C) will generally be of at most
- composition (C) preferably of at most 80 wt. %, more preferably of at most 75 and most preferably of at most 70 wt. %, based on the total weight of the composition (C).
- composition (C) of 40-80 wt. %, more preferably from 50-70 wt. % based on the total weight of the composition (C).
- the polymer (P) is preferably a silicon resin.
- silicon resin is intended to denote polymers more than 50 mol % of the recurring units of which contain silicon, carbon, hydrogen and oxygen, such as the one depicted below
- R's are equal or different from each other and chosen from alkyl groups.
- the silicone resin may be prepared by any general method. Typically, silicone resins are formed by hydrolytic condensation of various silicone precursors. Some starting materials used in the formation of silicone resins include but are not limited to sodium silicate, chlorosilane, tetraethoxysilane, ethyl polysilicate, dimethyldichlorosilane and disiloxanes.
- the silicon resin if the polymer composition (C) is not limited to a type of silicone material which is formed by branched, cage- like oligosiloxanes with the general formula of R n SiX m Oy, where R is a non-reactive substituent, e.g., methyl or phenyl group, and X is a functional group, e.g., hydrogen, hydroxyl, chlorine or alkoxy group.
- R is a non-reactive substituent
- X is a functional group, e.g., hydrogen, hydroxyl, chlorine or alkoxy group.
- the foregoing groups may be highly crosslinked to form insoluble polysiloxane structures.
- R is a methyl group
- four possible functional siloxane monomeric units include but are not limited to MesSiO, Me 2 Si0 2 , MeSiC and Si0 4 .
- Silicone resins also include silicone rubbers which are rubber-like material composed of silicone which is vulcanized through the introduction of heat.
- the vulcanization process may include more than one stage, e.g., heating to form a shape followed by a prolonged post-curing process.
- Silicone rubber can be colored and may further be extruded into tubes, strips, cords, etc., and such applications may be further used to form gaskets and o-rings.
- Some silicone polymers are formed by combining two or more components thereby resulting in a composition that may be crosslinked, cured or vulcanized.
- a silicone polymer may be formed from first and second silicone materials.
- the first silicone material may be an alkyl silicone polymer, e.g., methyl silicone
- the second silicone material may be a vinyl silicone polymer.
- the combination of the first and second silicone polymers is heat curable which may be accelerated with a catalyst such as platinum.
- the wt. % of the silicon resin in the polymer composition (C) is generally of at least 30 wt. %, preferably of at least 40 wt. %, more preferably of at least 50 wt. %, and most preferably of at least 60 wt. %, based on the total weight of the composition (C). It is further understood that the wt. % of the silicon resin in the polymer composition (C) will generally be of at least 30 wt. %, preferably of at least 40 wt. %, more preferably of at least 50 wt. %, and most preferably of at least 60 wt. %, based on the total weight of the composition (C). It is further understood that the wt. % of the silicon resin in the polymer composition (C) will generally be of at
- the polymer composition (C) of the present invention comprises from 5 to 40 wt. %, based on the total weight of the composition (C) of a flame retardant system.
- the flame retardant system may notably comprise at least one flame retardant selected from the group consisting of halogenated flame retardants and halogen free flame retardants.
- Halogenated flame retardants of various polymer compositions are well known in the art. They can be any halogenated compound that can provide flame retardant properties to the polymer compositions. They typically include chlorinated and/or brominated compounds and polymers.
- Notable halogenated flame retardants available on the market include but are not limited to 1 ,2-bis(tribromophenoxy)ethane, brominated epoxy oligomers, brominated polystyrene, chlorendic anhydride, chlorinated paraffins,
- decabromobiphenyl decabromodiphenylethane, decabromodiphenyloxide, dechlorane plus, dibromoneopentylglycol, ethylene-bis(5,6-dibromonorbornane- 2,30dicarboximide), ethylene-bis(tetrabromophthalimide), halogenated polyetherpolyols, hexabromocyclododecane, octabromodiphenyloxide, octabromotrimethylphenylindane, pentabromodiphenyloxide,
- the halogenated flame retardant is a brominated or chlorinated compound/polymer, more preferably a brominated compound/polymer, even more preferably a brominated compound/polymer with a bromine content of 50-70 weight %, relative to the weight of the brominated compound.
- the halogenated flame retardant is a halogenated polystyrene or halogenated polyphenylene ether.
- the halogenated flame retardant compound is a brominated polystyrene, still more preferably a polybromostyrene.
- the polymer composition (C) may also comprise, in addition to the halogenated flame retardant system, a flame retardant synergist (FRS-A).
- the flame retardant synergist (FRS-A) may comprise antimony trioxide, antimony dioxide, sodium antimonate, iron oxide, zinc phosphate and/or a metal salt of boric acid or stannic acid, wherein said metal is selected from the group consisting of zinc, an alkali metal (metal of group I of the Periodic Table) and an alkaline earth metal (metal of group II of the Periodic Table).
- Suitable metal salts of stannic acid include, for example, zinc stannate, zinc hydroxystannate, magnesium stannate, sodium stannate and potassium stannate.
- Suitable metal salts of boric acid include, for example, zinc borate, calcium borate and magnesium borate. Of these metal salts, zinc borate and zinc stannate, and mixtures thereof are preferred. More preferably, polymer composition (C) comprises sodium antimonate and/or zinc borate. The advantage of these preferred embodiments is that the color stability after retention at elevated temperature is even further enhanced.
- the flame retardant synergist (FRS-A) is preferably present in an amount of 0.1-20 wt. %, more preferably 1-15 wt. %, still more preferably 5-10 wt. %, relative to the total weight of the polymer composition (C).
- Halogen free flame retardants may also be present in the polymer composition (C) and are well known in the art.
- the polymer composition (C) may notably comprise at least one
- organophosphorous compound selected from the group consisting of phosphinic salts (phosphinates), diphosphinic salts (diphosphinates) and condensation products thereof.
- the organophosphorous compound is selected from the group consisting of phosphinic salt (phosphinate) of the formula (I), a diphosphinic salt (diphosphinate) of the formula (II) and condensation products thereof :
- R l s R 2 are identical or different and each of Ri and R 2 is a hydrogen or a linear or branched C1-C6 alkyl group or an aryl group;
- R 3 is a linear or branched CI -CIO alkylene group, a C6-C10 arylene group, an alkyl-arylene group, or an aryl-alkylene group;
- M is selected from calcium ions, magnesium ions, aluminum ions, zinc ions, titanium ions, and combinations thereof;
- m is an integer of 2 or 3;
- n is an integer of 1 or 3; and
- x is an integer of 1 or 2.
- Ri and R 2 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, and phenyl;
- R 3 is selected from methylene, ethylene, n-propylene, isopropylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene, phenylene, naphthylene,
- Phosphinates are preferred as organophosphorous compound. Suitable phosphinates have been described in US 6,365,071. Particularly preferred phosphinates are aluminum phosphinates, calcium phosphinates, and zinc phosphinates. Excellent results were obtained with aluminum phosphinates. Among aluminum phosphinates, aluminium ethylmethylphosphinate and aluminium diethylphosphmate and combinations thereof are preferred. Excellent results were in particular obtained when aluminium diethylphosphmate was used.
- the polymer composition (C) may also comprise, in addition to the halogen free flame retardant, a flame retardant synergist (FRS-B), preferably nitrogen-containing synergists.
- a flame retardant synergist FSS-B
- nitrogen-containing synergists preferably nitrogen-containing synergists.
- the nitrogen-containing synergists preferably comprise benzoguanamine, tris(hydroxyethyl) isocyanurate, allantoin, glycoluril, melamine, melamine cyanurate, dicyandiamide, guanidine, carbodiimides, and condensation products thereof.
- the nitrogen-containing synergists preferably comprise condensation products of melamine.
- condensation products of melamine are melem, melam, or melon, or compounds of this type with a higher condensation level, or else a mixture of the same, and, by way of example, may be prepared by the process described in US 5,985,960.
- the phosphorus/nitrogen-containing synergists may comprise reaction products of melamine with phosphoric acid or with condensed phosphoric acids, or comprise reaction products of condensation products of melamine with phosphoric acid or condensed phosphoric acids, or else comprise a mixture of the specified products.
- the reaction products of melamine with phosphoric acid or with condensed phosphoric acids are compounds which arise via reaction of melamine or of the condensed melamine compounds, such as melam, melem, or melon etc., with phosphoric acid.
- these are dimelamine phosphate, dimelamine pyrophosphate, melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melam polyphosphate, melon polyphosphate, and melem polyphosphate, and mixed polysalts, e.g. those described in US 6,121,445 and US 6,136,973.
- the phosphorus/nitrogen-containing synergist may also be ammonium hydrogenophosphate, ammonium
- dihydrogenophosphate or ammonium polyphosphate.
- the flame retardant synergist (FRS-B) is preferably present in an amount of 0.1-10 wt. %, more preferably 0.5-8 wt. %, still more preferably 1-5 wt. %, relative to the total weight of the polymer composition (C).
- the polymer composition (C) of the present invention comprises from 5 to 30 wt. % of a flame retardant system, based on the total weight of the polymer composition (C).
- the flame retardant system is present in the total weight of the polymer composition (C) in an amount of preferably at least 8 wt. %, more preferably of at least 10 wt. %, still more preferably of at least 12 wt. % and most preferably of at least 13 wt. %.
- the wt. % of the flame retardant system in the total weight of the polymer composition (C) is preferably of at
- the polymer composition (C) of the present invention comprises from 1 to 7 wt. %, based on the total weight of the composition (C) of magnesium oxide.
- the magnesium oxide is present in the total weight of the polymer composition (C) in an amount of preferably at least 2, more preferably of at least 2.5, still more preferably of at least 2.75 and most preferably of at least 3 wt. %. Besides, the magnesium oxide is present in the total weight of the polymer composition (C) in an amount of preferably at most 6, more preferably of at most 5.5, still more preferably of at most 5 and most preferably of at most 4.5 wt. %. Excellent results were obtained when the magnesium oxide was present in the total weight of the polymer composition (C) in an amount of from 3 to 5 wt. %.
- the polymer composition (C) may also comprise at least one white pigment.
- the white pigment is preferably selected from the group consisting of Ti0 2 , ZnS 2 and BaS0 4 .
- the shape of the particles is not particularly limited ; they may be notably round, flaky, flat, and so on.
- the white pigment is preferably titanium dioxide (Ti0 2 ).
- the form of titanium dioxide is not particularly limited and a variety of crystalline forms such as the anatase form, the rutile form, and the monoclinic type can be used.
- Titanium dioxide may or may not be treated with a surface treatment agent.
- the weight-average particle size of the titanium oxide is in the range of 0.15 ⁇ to 0.35 ⁇ .
- the surface of the titanium dioxide particles will preferably be coated.
- the titanium dioxide will preferably be first coated with an inorganic coating and then with an organic coating.
- the titanium dioxide particles may be coated using any method known in the art.
- Preferred inorganic coatings include metal oxides.
- Organic coatings may include one or more of carboxylic acids, polyols, alkanolamines, and/or silicon compounds.
- the white pigment is preferably present in an amount of at least 1 wt. %, preferably of at least 6 wt. %, more preferably of at least 8 wt. %, even more preferably of at least 10 wt. %, and most preferably of at least 15 wt. %, based on the total weight of the polymer composition (C).
- the white pigment is also preferably present in an amount of at most 50 wt. %, preferably of at most 45 wt. %, more preferably of at most 40 wt. %, even more preferably of at most 35 wt. %, and most preferably of at most 30 wt. %, based on the total weight of the polymer composition (C).
- the polymer composition (C) may also comprise other polymers than the above mentioned polymers (P) such as polycarbonate, polyethylene glycol, polysulfone, PEEK and PTFE.
- the polymer composition (C) may also further comprise at least one reinforcing filler.
- Reinforcing fillers are preferably fibrous. More preferably, the reinforcing filler is selected from glass fiber, carbon fiber, synthetic polymeric fiber, aramid fiber, aluminum fiber, titanium fiber, magnesium fiber, boron carbide fibers, rock wool fiber, steel fiber, wollastonite, etc. Still more preferably, it is selected from glass fiber and wollastonite.
- a particular class of fibrous fillers consists of whiskers, i.e. single crystal fibers made from various raw materials such as SiC, BC, Fe and Ni.
- whiskers i.e. single crystal fibers made from various raw materials such as SiC, BC, Fe and Ni.
- glass fibers are preferred; they include chopped strand A-, E-, C-, D-, S- T- and R-glass fibers, as described in chapter 5.2.3, p. 43-48 of Additives or Plastics Handbook, 2nd ed., John Murphy.
- Glass fibers may have a round cross-section or an elliptic cross-section (also called flat fibers).
- the reinforcing filler is preferably present in an amount of at least 2 wt. %, more preferably at least 4 wt. %, still more preferably at least 5 wt. %, and most preferably at least 10 wt. %, based on the total weight of the polymer composition (C).
- the reinforcing filler is also preferably present in an amount of at most 40 wt. %, more preferably at most 30 wt. %, still more preferably at most 25 wt. %, and most preferably at most 20 wt. %, based on the total weight of the polymer composition (C).
- the polymer composition (C) can further contain one or more impact modifiers.
- the impact modifiers can be reactive with the polymer (P) or non- reactive.
- the polymer composition (C) contains at least one reactive impact modifier and at least one non-reactive impact modifier.
- Reactive impact modifiers that may be used include ethylene-maleic anhydride copolymers, ethylene-alkyl (meth)acrylate-maleic anhydride copolymers, ethylene-alkyl (meth)acrylate-glycidyl (meth)acrylate copolymers, and the like.
- An example of such reactive impact modifier is a random terpolymer of ethylene, methylacrylate and glycidyl methacrylate.
- Non-reactive impact modifiers that may be blended into the polymer composition (C) generally include various rubber materials, such as acrylic rubbers, ASA rubbers, diene rubbers, organosiloxane rubbers, EPDM rubbers, SBS or SEBS rubbers, ABS rubbers, NBS rubbers and the like.
- Particular examples of non-reactive impact modifiers include ethyl butylacrylate, ethyl (methyl)acrylate or 2 ethyl hexyl acrylate copolymers.
- the impact modifier is preferably present in an amount of at least 2 wt. %, more preferably at least 4 wt. %, still more preferably at least 5 wt. %, and most preferably at least 10 wt. %, based on the total weight of the polymer composition (C).
- the impact modifier is also preferably present in an amount of at most 20 wt. %, more preferably at most 15 wt. %, still more preferably at most 10 wt. %, and most preferably at most 5 wt. %, based on the total weight of the polymer composition (C).
- the polymer composition (C) may optionally further contain up to about 3 wt. % of ultraviolet light stabilizers or UV blockers, based on the total weight of the polymer composition (C).
- ultraviolet light stabilizers include triazoles and triazines, oxanilides, hydroxybenzophenones, benzoates, and a-cyanoacrylates.
- the ultraviolet light stabilizers are preferably present in an amount of about 0.1 to about 3 wt. %, or preferably about 0.1 to about 1 wt. %, or more preferably about 0.1 to about 0.6 wt. %, of the total weight of the polymer composition (C).
- the polymer composition (C) may also comprise other optional ingredients such as mold release agents, lubricants, nucleating agents, plasticizers, optical brighteners and other stabilizers, different from the ones described above.
- the polymer composition (C) may comprise talc as a nucleating agent.
- the talc is preferably present in an amount of about 0.5 to about 3 wt. %, or preferably about 0.8 to about 1.2 wt. %, or more preferably about 1 wt. %, of the total weight of the polymer composition (C).
- melt-mixing method may be used to combine the polymeric components and non-polymeric ingredients to prepare the polymer
- composition (C) the polymeric components and non-polymeric ingredients may be added to a melt mixer, such as, for example, a single or twin- screw extruder, a blender or a Banbury mixer, either all at once through a single step addition, or in a stepwise fashion, and then melt-mixed.
- a melt mixer such as, for example, a single or twin- screw extruder, a blender or a Banbury mixer, either all at once through a single step addition, or in a stepwise fashion, and then melt-mixed.
- a melt mixer such as, for example, a single or twin- screw extruder, a blender or a Banbury mixer, either all at once through a single step addition, or in a stepwise fashion, and then melt-mixed.
- the terms "light emitting diode device” and “LED device” intend to denote a device comprising at least one light emitting diode, an electrical connection capable of connecting the diode to an electrical circuit, and a housing partially surrounding the diode.
- the LED device may optionally have a lens that fully or partially covers the LED.
- LEDs are preferably chosen from the group of top view LEDs, side view LEDs and power LEDs.
- the top view LEDs are notably used in automotive lighting applications such as panel displays, stop lights and turn signals.
- the side view LEDs are notably used for mobile appliance applications such as, for example, cell phones and PDAs.
- the power LEDs are notably used in flashlights, automotive day light running lights, signs and as backlight for LCD displays and TVs.
- the part of LED device according to the present invention may be incorporated into LED devices used in applications such as traffic signals, large area displays, video screens, interior and exterior lighting, cellular telephone display backlights, automotive displays, vehicle brake lights, vehicle head lamps, laptop computer display backlights, pedestrian floor illumination and flashlights.
- the articles of the present invention are preferably parts of LED devices such as housings, reflectors and heatsinks.
- the part of LED device comprising the polymer composition (C) may be manufactured by any suitable method known to those skilled in the art for melt- processing composition (C), such as injection molding or the like.
- the part of LED device of the invention may be overmolded over a metal (such as copper or silver-coated copper) lead frame that can be used to make an electrical connection to a LED inserted into the housing.
- the part of LED device of the invention preferably has a cavity in the portion of the housing that surrounds the LED, which serves to reflect the LED light in the outward direction and towards a lens, if one is present.
- the cavity may be in a cylindrical, conical, parabolic or other curved form, and preferably has a smooth surface.
- the walls of the cavity may be parallel or substantially parallel to the diode.
- a lens may be formed over the diode cavity and may comprise an epoxy or silicone material.
- At least 50 wt. % and more preferably more than 80 wt. % of the part comprises the polymer composition (C) (the part can possibly further contain notably a metal ; for example, for certain end uses, the surface of the part acting as reflector may be metal plated). More preferably, more than 90 wt. % of the part comprises the polymer composition (C). Still more preferably, the part consists essentially of the polymer composition (C). The most preferably, the part consists of the polymer composition (C).
- Glass fiber OCV 995 from OCVTM Reinforcements. Titanium Dioxide : TIPAQUE PC-3 available from Ishihara Sangyo Kaisha, Ltd.
- Magnesium oxide KYOWAMAG MF-150 available from Kyowa Chemical Industry Co Ltd.
- Halogen free flame retardant EXOLIT ® OP 1230 FR from Clariant Corp, which is an organic phosphinate.
- Halogenated flame retardant package The four following ingredients were used in the ratio 82.25/13.55/1.30/2.90, PDBS 80 from Chemtura (homopolymer of dibromostyrene), Pyroblock SAP-2 from Chemtura (sodium antimonate synergist), calcium oxide CA602 from Atlantic Equipment Engineers and Primacor 1410 from Entec Polymers LLC which is an ethylene acrylic acid copolymer.
- PDBS 80 from Chemtura (homopolymer of dibromostyrene)
- Pyroblock SAP-2 from Chemtura (sodium antimonate synergist)
- calcium oxide CA602 from Atlantic Equipment Engineers
- Primacor 1410 from Entec Polymers LLC which is an ethylene acrylic acid copolymer.
- Hindered amine : NYLOSTAB ® SEED stabilizer is a hindered amine commercially available from Clariant Corp.
- Antioxidant ADK AO-80 from Amfine Chemical Corporation is a hindered phenolic antioxidant
- LLDPE LLDPE GRSN-9820 NT 7 commercially available from DOW.
- the polyamide resin described above was fed to the first barrel of a
- ZSK-26 twin screw extruder comprising 12 zones via a loss in weight feeder.
- the barrel set-point temperatures were in the range of 240-330°C and the resins were melted before zone 5.
- the other ingredients were fed at zone 5 through a side stuffer via a loss in weight feeder.
- the screw rate was 175 rpm.
- the extrudates were cooled and pelletized using conventional equipment. The nature and quantity of the various ingredients used are summarized in Table 1, indicating the amount of each ingredient in wt. %.
- a 20 mm vertical burning test was carried out according to UL Standard 94 which identifies test methods for f ammability of plastic materials for parts in devices and appliances.
- a set of 5 - 0.79 mm thick - plastic specimens molded from compositions E-l, CE-2, E-3 and CE-4 were subjected to a 20mm flame in accordance with the prescribed test procedures. The blue flame was applied centrally to the middle point of the bottom edge of the specimens for three seconds. The flame was then withdrawn and the afterflamme time (ti) was measured. The procedure was repeated and the afterflamme time (t 2 ) was also measured. The sum of all afterflamme times were added up and also reported in Table 2.
- composition according to the present invention E-l and E-3 surprisingly show higher retention of reflectivity as molded and after exposure to high heat compared to comparative examples CE-2, and CE-4, while at the same time featuring exceptional flame resistance.
- compositions according to the present invention achieve outstanding optical properties both on the molded article as such and the same article having been submitted to thermal treatment, which is intended to mimic conditions to which the materials might be exposed during the manufacture of LED devices.
- the compositions according to the present invention achieve also excellent flame resistance, showing reduced afterflamme times when compared to the same compositions not comprising magnesium oxide (CE-2 and CE-4).
- Comparative examples CE-2 and CE-4 provide thus evidence that the flame retardant system alone is not enough in providing the outstanding optical properties obtained with the examples according to the invention.
- Example E-3 which combines both a halogenated flame retardant system and magnesium oxide, achieves unexpected results in terms of retention of reflectivity after high heat exposure and very low total afterflamme times.
- Examples E-l and E-3 according to the present invention comply thus with a wide set of requirements as set forth previously (notably good processability, high dimensional stability, high mechanical strength) and also surprisingly features a good reflectance after high heat treatment. Those compositions are therefore excellent candidates for the manufacture of LED components.
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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KR1020167013045A KR20160083011A (en) | 2013-11-06 | 2014-11-03 | Flame retardant led for indoor lighting |
US15/034,108 US20160272779A1 (en) | 2013-11-06 | 2014-11-03 | Flame retardant led for indoor lighting |
CN201480061125.3A CN105705561A (en) | 2013-11-06 | 2014-11-03 | Flame retardant LED for indoor lighting |
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US201361900670P | 2013-11-06 | 2013-11-06 | |
US61/900,670 | 2013-11-06 |
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WO2015067563A1 true WO2015067563A1 (en) | 2015-05-14 |
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PCT/EP2014/073586 WO2015067563A1 (en) | 2013-11-06 | 2014-11-03 | Flame retardant led for indoor lighting |
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US (1) | US20160272779A1 (en) |
KR (1) | KR20160083011A (en) |
CN (1) | CN105705561A (en) |
TW (1) | TW201529678A (en) |
WO (1) | WO2015067563A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3606988A4 (en) * | 2017-04-07 | 2020-11-25 | Imerys Talc America, Inc. | Flame-retardant polymer composition |
EP3372631B1 (en) | 2017-03-08 | 2021-06-16 | Armacell Enterprise GmbH & Co. KG | Flexible foam with improved insulation properties |
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CN106554605A (en) * | 2016-11-01 | 2017-04-05 | 常州大学 | A kind of phosphorus bromine synergistic highly expanded flame-retardant PET material and preparation method thereof |
EP3911696A1 (en) * | 2019-01-16 | 2021-11-24 | Clariant International Ltd | Flame retardant mixture |
CN111592754B (en) * | 2020-05-27 | 2022-05-24 | 杭州本松新材料技术股份有限公司 | Brominated flame-retardant polyamide composition and preparation method thereof |
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2014
- 2014-11-03 CN CN201480061125.3A patent/CN105705561A/en active Pending
- 2014-11-03 KR KR1020167013045A patent/KR20160083011A/en not_active Withdrawn
- 2014-11-03 US US15/034,108 patent/US20160272779A1/en not_active Abandoned
- 2014-11-03 WO PCT/EP2014/073586 patent/WO2015067563A1/en active Application Filing
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EP3606988A4 (en) * | 2017-04-07 | 2020-11-25 | Imerys Talc America, Inc. | Flame-retardant polymer composition |
Also Published As
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US20160272779A1 (en) | 2016-09-22 |
CN105705561A (en) | 2016-06-22 |
KR20160083011A (en) | 2016-07-11 |
TW201529678A (en) | 2015-08-01 |
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